Graft polymer with sidechains comprising nitrogen heterocycles

ABSTRACT

Graft polymer, comprising (A) a polymer graft skeleton with no mono-ethylenic unsaturated units and (B) polymer sidechains formed from co-polymers of two different mono-ethylenic unsaturated monomers (B1) and (B2), each comprising a nitrogen-containing heterocycle, whereby the proportion of the sidechains (B) amounts to more than 55 wt. % of the total polymer.

The present invention relates to graft polymers containing

-   -   (A) a polymeric grafting base devoid of monoethylenically        unsaturated units, and    -   (B) polymeric side chains formed from copolymers of two        different monoethylenically unsaturated monomers (B1) and (B2)        which each contain at least one nitrogeneous heterocycle,

wherein said side chains (B) account for more than 55% by weight of thetotal polymer.

This invention further relates to the making of these graft polymers andto their use as dye transfer inhibitors in laundry detergents.

Dyed textiles often shed dye molecules during washing, and these dyemolecules then go onto other textiles. This dye transfer is undesirable,and dye transfer inhibitor chemicals are used to counteract it.

DE-A-195 19 339 discloses copolymers of vinylimidazole andN-vinylpyrrolidine which are useful as dye transfer inhibitors.

CA-A-2 227 484 describes block or random copolymers of unsaturatedanionic or nonionic monomers, vinylimidazole and N-vinylpyrrolidone asuseful ingredients for laundry detergent compositions having a DTIeffect.

DE-A-100 36 713 claims dye transfer inhibitors which are based on graftpolymers having polyethylene glycol as a grafting base andvinylimidazole and N-vinylpyrrolidone as a graft component and in whichthe weight ratio of graft component to grafting base is in the rangefrom 0.1 to 1.2:1. However, what is explicitly disclosed is only a graftpolymer in which the graft component fraction is 20% by weight.

Known dye transfer inhibitors have a number of disadvantages. First,their performance is often not good enough and, what is more, highlydependent on the composition of the laundry detergent. Secondly, theyare not compatible with all customary laundry detergent components, sothat the laundry detergent composition is subject to severe constraints,which is problematical in the case of liquid detergents in particular.

It is an object of the present invention to remedy these defects andprovide dye transfer inhibitors having advantageous applicationproperties.

We have found that this object is achieved by graft polymers containing

-   -   (A) a polymeric grafting base devoid of monoethylenically        unsaturated units, and    -   (B) polymeric side chains formed from copolymers of two        different monoethylenically unsaturated monomers (B1) and (B2)        which each contain at least one nitrogeneous heterocycle,        wherein said side chains (B) account for more than 55% by weight        of the total polymer.

Preferred graft polymers are disclosed in subsidiary claims.

The present invention further provides a process for preparing the graftpolymers, which comprises free-radically polymerizing the monomers (B1)and (B2) in the presence of the grafting base (A).

Lastly the present invention provides for the use of the graft polymersas dye transfer inhibitors in laundry detergents.

The graft polymers of the invention, which have a comblike construction,are characterized by an optimum ratio of side chains (B) to backbone(grafting base (A)). This ratio is optimum when the fraction of the sidechains (B) accounts for more than 55% by weight of the graft polymers.It is only then that side chain density and length are sufficient. Thefraction is preferably in the range from 60 to 95% by weight, morepreferably in the range from 70 to 95% by weight and most preferably inthe range from 70 to 90% by weight.

Monomer (B1) in the side chains (B) of the graft polymers according tothe invention is preferably a cyclic N-vinylamide of the general formulaI

where

-   R is C₁–C₅-alkyl and-   R¹ is hydrogen or C₁–C₄-alkyl.

Specific examples of monomers useful as monomer (B1) areN-vinylpyrrolidone, N-vinylvalerolactam and N-vinylcaprolactam, of whichN-vinylpyrrolidone is preferred.

The side chains (B) preferably further contain units derived from amonoethylenically unsaturated comonomer (B2) which contains anitrogenous heterocycle selected from the group consisting of thepyrroles, pyrrolidines, pyridines, quinolines, isoquinolines, purines,pyrazoles, imidazoles, triazoles, tetrazoles, indolizines, pyridazines,pyrimidines, pyrazines, indoles, isoindoles, oxazoles, oxazolidones,oxazolidines, morpholines, piperazines, piperidines, isoxazoles,thiazoles, isothiazoles, indoxyls, isatins, dioxindoles and hydantoinsand derivatives thereof, for example barbituric acid and uracil andderivatives thereof.

Preferred heterocycles are imidazoles, pyridines and pyridine N-oxides,of which imidazoles are particularly preferred.

Examples of particularly suitable comonomers (B2) are N-vinylimidazoles,alkylvinylimidazoles, especially methylvinylimidazoles such as1-vinyl-2-methylimidazole, 3-vinylimidazole N-oxide, 2- and4-vinylpyridines, 2- and 4-vinylpyridine N-oxides and also betainicderivatives and quaternization products thereof.

Very particularly preferred comonomers (B2) are N-vinylimidazoles of thegeneral formula IIa, betainic N-vinylimidazoles of the general formulaIIb, 2- and 4-vinylpyridines of the general formulae IIc and IId andalso betainic 2- and 4-vinylpyridines of the general formulae IIe andIIf

where

-   R², R³, R⁴ and R⁶ are each independently hydrogen, C₁–C₄-alkyl or    phenyl, preferably hydrogen;-   R⁵ is C₁–C₂₀-alkylene, preferably C₁–C₂-alkylene;-   X⁻ is —SO₃ ⁻, —OSO₃ ⁻, —COO⁻, —OPO(OH)O⁻, —OPO(OR′)O⁻ or —PO(OH)O⁻;-   R′ is C₁–C₆-alkyl.

Examples of especially preferred betainic comonomers (B2) areunsubstituted monomers of the formulae IIb, IIe and IIf where the R⁵—X⁻moiety is —CH₂—COO⁻ or —C₂H₄—SO₃ ⁻.

It will be appreciated that vinylimidazoles and vinylpyridinesquaternized before or after polymerization are likewise suitable for useas comonomers (B2).

The quaternization can be effected in particular with alkylating agentssuch as alkyl halides, which generally have from 1 to 24 carbon atoms inthe alkyl moiety, or dialkyl sulfates, which generally contain alkylmoieties of from 1 to 10 carbon atoms. Examples of suitable alkylatingagents from these groups are methyl chloride, methyl bromide, methyliodide, ethyl chloride, ethyl bromide, propyl chloride, hexyl chloride,dodecyl chloride and lauryl chloride on the one hand and dimethylsulfate and diethyl sulfate on the other. Suitable alkylating agentsfurther include for example benzyl halides, especially benzyl chlorideand benzyl bromide; chloroacetic acid; methyl fluorosulfate;diazomethane; oxonium compounds, such as trimethyloxoniumtetrafluoroborate; alkylene oxides, such as ethylene oxide, propyleneoxide and glycidol, which are used in the presence of acids; cationicepichlorohydrins. Preferred quaternizing agents are methyl chloride,dimethyl sulfate and diethyl sulfate.

Examples of particularly suitable quaternized comonomers (B2) are1-methyl-3-vinylimidazolium methosulfate and 1-methyl-3-vinylimidazoliummethochloride.

The weight ratio of the monomers (B1) and (B2) is generally in the rangefrom 99:1 to 1:99, preferably in the range from 90:10 to 30:70, morepreferably in the range from 90:10 to 50:50, most preferably in therange from 80:20 to 50:50 and especially in the range from 80:20 to60:40.

The polymeric grafting base (A) of the graft polymers according to theinvention is preferably formed by a polyether. The term “polymeric” asused herein shall also comprehend oligomeric compounds.

The polyethers (A) preferably have an average molecular weight M_(n) ofat least 300 and the general formula IIIa.

or IIIb

where:

-   R⁷ is hydroxyl, amino, C₁–C₂₄-alkoxy, R¹³—COO—, R¹³—NH—COO— or a    polyalcohol radical,-   R⁸ R⁹ and R¹⁰ which may be the same or different, are each —(CH₂)₂—,    —(CH₂)₃—, —(CH₂)₄—, —CH₂—CH(CH₃)—, —CH₂—CH(CH₂—CH₃)— or    —CH₂—CHOR¹⁴—CH₂—,-   R¹¹ is hydrogen, amino-C₁–C₆-alkyl, C₁–C₂₄-alkyl, R¹³—CO— or    R¹³—NH—CO—,-   R¹² is C₁–C₂₀-alkylene whose carbon chain may be interrupted by from    1 to 10 oxygen atoms in ether function,-   R¹³ is C₁–C₂₄-alkyl,-   R¹⁴ is hydrogen, C₁–C₂₄-alkyl or R¹³—CO—,-   A is —CO—O—, —CO—B—CO—O— or —CO—NH—B—NH—CO—O—;-   B is —(CH₂)_(t)— or substituted or unsubstituted arylene,-   n is 1 or, when R⁷ is a polyalcohol radical, is from 1 to 8,-   s is from 0 to 500;-   t is from 1 to 12;-   each u, which may be the same or different, is from 1 to 5000,-   each v, which may be the same or different, is from 0 to 5000, and-   each w, which may be the same or different, is from 0 to 5000.

The polyethers of the formula IIIa are a preferred grafting base (A).

The grafting base (A) comprises polyethers from the group of thepolyalkylene oxides based on ethylene oxide, propylene oxide andbutylene oxides, polytetrahydrofuran and also polyglycerol. Depending onthe nature of the monomeric building blocks, the resulting polymers willcontain the following structural units:

-   —(CH₂)₂—O—, —(CH₂)₃—O—, —(CH₂)₄—O—, —CH₂—CH(CH₃)—O—,    —CH₂—CH(CH₂—CH₃)—O—, —CH₂—CHOR⁸—CH₂—O—

Also suitable are not only homopolymers but also copolymers, andcopolymers can have a random distribution or be block polymers.

The terminal primary hydroxyl groups of the polyethers prepared on thebasis of alkylene oxides or glycerol and also the secondary OH groups ofpolyglycerol can be free or etherified with C₁–C₂₄ alcohols, esterifiedwith C₁–C₂₄ carboxylic acids or urethanized with isocyanates. Usefulalcohols for this purpose include for example primary aliphaticalcohols, such as methanol, ethanol, propanol, and butanol, primaryaromatic alcohols, such as phenol, isopropylphenol, tert-butylphenol,octylphenol, nonylphenol and naphthol, secondary aliphatic alcohols,such as isopropanol, tertiary aliphatic alcohols, such as tert-butanol,and polyhydric alcohols, for example diols, such as ethylene glycol,diethylene glycol, propylene glycol, 1,3-propanediol and butanediol, andtriols, such as glycerol and trimethylolpropane. However, the hydroxylgroups may also be exchanged for primary amino groups by reductiveamination with hydrogen-ammonia mixtures under superatmospheric pressureor have been converted into aminopropylene end groups by cyanoethylationwith acrylonitrile and hydrogenation. The hydroxyl end groups may becapped or tipped subsequently by reaction with alcohols or with alkalimetal hydroxide solutions, amines and hydroxylamines, but thesecompounds, like Lewis acids, for example boron trifluoride, can also beused as starters at the start of the polymerization. Finally, thehydroxyl groups can also be capped or tipped by reaction with alkylatingagents, such as dimethyl sulfate.

The alkyl radicals in the formulae IIIa and IIIb can be branched orunbranched C₁–C₂₄-alkyl radicals, of which C₁–C₁₂-alkyl radicals arepreferred and C₁–C₆-alkyl radicals are particularly preferred. Examplesare methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl,2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl,2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl,n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl,2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl,1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl,2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl,1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl,1-ethyl-2-methylpropyl, n-heptyl, 2-ethylhexyl, n-octyl, n-nonyl,n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl,n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-eicosyl.

The average molecular weight M_(n) of the polyethers (A) is at least 300and is generally≦100 000. It is preferably in the range from 500 to 50000, more preferably in the range from 500 to 10 000 and most preferablyin the range from 500 to 2 000.

It is advantageous to use homo- and copolymers of ethyleneoxide,propylene oxide, butylene oxide and isobutylene oxide, which can belinear or branched, as grafting base (A). The term homopolymers as usedherein shall for the purposes of the invention also comprehend thosepolymers which, as well as the polymerized alkylene oxide unit,additionally contain reactive molecules which were used for initiatingthe polymerization of the cyclic ethers or for end group capping of thepolymer.

Branched polymers can be prepared by for example adding to low molecularweight polyalcohols (R⁷ radicals in the formulae IIIa and IIIb), forexample pentaerythritol, glycerol and sugars or sugar alcohols, such assucrose, D-sorbitol and D-mannitol, disaccharides, ethylene oxide and,if desired, propylene oxide and/or butylene oxides or else polyglycerol.

In the polymers formed, at least one, preferably from one to eight andmore preferably from one to five of the hydroxyl groups present in thepolyalcohol molecule can be linked in the form of an ether bond to thepolyether radical of the formula IIIa or IIIb.

Four-arm polymers are obtainable by adding the alkylene oxides todiamines, preferably ethylenediamine.

Further branched polymers are preparable by reacting alkylene oxideswith higher amines, for example triamines, or especiallypolyethyleneimines. Suitable polyethyleneimines for this generally haveaverage molecular weights M_(n) in the range from 300 to 20 000,preferably in the range from 500 to 10 000 and more preferably in therange from 500 to 5 000. The weight ratio of alkylene oxide topolyethyleneimine is customarily in the range from 100:1 to 0.1:1, andpreferably in the range from 20:1 to 0.5:1.

However, it is also possible to use polyesters of polyalkylene oxidesand aliphatic C₁–C₁₂-, preferably C₁–C₆-, dicarboxylic acids or aromaticdicarboxylic acids, for example oxalic acid, succinic acid, adipic acidor terephthalic acid, having average molecular weights of from 1 500 to25 000 as grafting base (A).

It is further possible to use phosgenation-prepared polycarbonates ofpolyalkylene oxides or else polyurethanes of polyalkylene oxides andaliphatic C₁–C₁₂-diisocyanates and preferably C₁–C₆-diisocyanates oraromatic diisocyanates, for example hexamethylene diisocyanate orphenylene diisocyanate, as grafting base (A).

These polyesters, polycarbonates or polyurethanes can contain up to 500,preferably up to 100 polyalkylene oxide units, in which casepolyalkylene oxide units can consist not only of homopolymers but alsoof copolymers of different alkylene oxides.

Grafting base (A) is particularly preferably selected from homo- andcopolymers of ethylene oxide and/or propylene oxide, which can be singlyor doubly end group capped or tipped.

The particular advantage of polypropylene oxide and copolymeric alkyleneoxides having a high propylene oxide fraction is that grafting takesplace easily.

The particular advantage of polyethylene oxide and copolymeric alkyleneoxides with a high ethylene oxide fraction is that, after grafting hastaken place and has produced a graft polymer having the same graftdensity as polypropylene oxide, the weight ratio of side chain tografting base is larger.

The K values of the graft polymers according to the invention arecustomarily in the range from 10 to 150, preferably in the range from 10to 80 and more preferably in the range from 15 to 60 (determined afterH. Fikentscher, Cellulose-Chemie, Volume 13, pages 58 to 64 and 71 to 74(1932) in water or aqueous sodium chloride solutions at 25° C. andpolymer concentrations ranging from 0.1% by weight to 5% by weight,depending on the K value range). The particular K value desired can beset in a conventional manner through the composition of the startingmaterials.

The invention likewise provides a process for preparing the graftpolymers, which comprises free-radically polymerizing the monomers (B1)and (B2) in the presence of the grafting base (A).

The polymerization can be carried out for example in solutionpolymerization, bulk polymerization, as an emulsion polymerization, asan inverse emulsion polymerization, as a suspension polymerization, asan inverse suspension polymerization or as a precipitationpolymerization. Preference is given to bulk polymerization andespecially solution polymerization, which is carried out in the presenceof water in particular.

A bulk polymerization can be carried out by dissolving the monomers (B1)and (B2) in the grafting base (A), heating the mixture to thepolymerization temperature and adding a free-radical initiator beforepolymerizing the mixture to completion. The polymerization can also becarried out semicontinuously by initially charging a portion, forexample 10% by weight, of the mixture of grafting base (A), monomer(B1), monomer (B2) and free-radical initiator and heating the mixture tothe polymerization temperature and, after the polymerization has lightedoff, to add the rest of the mixture to be polymerized at a ratecommensurate with the progress of the polymerization. However, it isalso possible to initially charge the grafting base (A) to a reactor, toheat the initial charge to polymerization temperature and to addmonomers (B1) and (B2) separately or as a mixture and the free-radicalinitiator either all at once, batchwise or preferably continuouslybefore polymerizing.

It will be appreciated that the above-described graft polymerization canalso be carried out in a solvent. Suitable organic solvents are forexample aliphatic and cycloaliphatic monohydric alcohols, such asmethanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol,tert-butanol, n-hexanol and cyclohexanol, polyhydric alcohols, forexample glycols, such as ethylene glycol, propylene glycol and butyleneglycol, and glycerol, alkyl ethers of polyhydric alcohols, for examplemethyl and ethyl ethers of the dihydric alcohols mentioned, and alsoethyl alcohols, such as diethylene glycol and triethylene glycol, andalso cyclic ethers, such as dioxane.

According to the invention, the graft polymerization is preferablycarried out in water as a solvent. The components (A), (B1) and (B2) aremore or less effectively dissolved, depending on the amount of waterused. The water, in part or in whole, can also be added in the course ofthe polymerization. It will be appreciated that it is also possible touse mixtures of water and the abovementioned organic solvents.

It is customary to use from 5 to 250% by weight and preferably from 10to 150% by weight of organic solvent, water or mixture of water andorganic solvent, based on the graft polymer.

The polymerization in water generally provides 10–70% by weight andpreferably 20–50% by weight solutions or dispersions of the graftpolymers according to the invention, which if desired can be convertedinto powder form by means of various drying processes, for example spraydrying, fluidized spray drying, drum drying or freeze drying. An aqueoussolution or dispersion can then easily be reestablished by adding waterat the desired time.

Useful free-radical initiators are in particular peroxo compounds, azocompounds, redox initiator systems and reducing compounds. It will beappreciated that it is also possible to use mixtures of free-radicalinitiators.

Examples of suitable free-radical initiators are specificallyalkalimetalperoxodisulfates, for example sodium peroxodisulfate,ammonium peroxodisulfate, hydrogen peroxide, organic peroxides, such asdiacetal peroxide, di-tert-butyl peroxide, diamyl peroxide, dioctanoylperoxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide,bis(o-tolyl) peroxide, succinyl peroxide, tert-butyl peracetate,tert-butyl permaleate, tert-butyl perisobutyrate, tert-butylperpivalate, tert-butyl peroctoate, tert-butyl perneodecanoate,tert-butyl perbenzoate, tert-butyl peroxide, tert-butyl hydroperoxide,cumene hydroperoxide, tert-butyl peroxi-2-ethylhexanoate and diisopropylperoxidicarbamate; azobisisobutyronitrile, azobis(2-amidopropane)dihydrochloride and 2,2′-azobis(2-methylbutyronitrile); sodium sulfite,sodium bisulfite, sodium formaldehydesulfoxylate and hydrazine andcombinations thereof with hydrogen peroxide; ascorbic acid/iron(II)sulfate/sodium peroxodisulfate, tert-butyl hydroperoxide/sodiumdisulfite and tert-butyl hydroperoxide/sodium hydroxymethanesulfinate.

Preferred free-radical initiators are for example tert-butylperpivalate, tert-butyl peroctoate, tert-butyl perneodecanoate,tert-butyl peroxide, tert-butyl hydroperoxide,azobis(2-methylpropionamidine) dihydrochloride,2,2′-azobis(2-methylbutyronitrile), hydrogen peroxide and sodiumeroxodisulfate, to which redox metal salts, for example iron salts, canbe added in small amounts.

It is customary to use from 0.01 to 10% by weight and preferably from0.1 to 5% by weight of free-radical initiator, based on the onomers (B1)and (B2).

If desired, it is also possible to use polymerization regulators. Usefulcompounds are known to one skilled in the art and include for examplesulfur compounds, such as mercaptoethanol, 2-ethylhexyl thioglycolate,thioglycolic acid and dodecyl mercaptan. When polymerization regulatorsare used, their use level is generally in the range from 0.1 to 15% byweight, preferably in the range from 0.1 to 5% by weight and morepreferably in the range from 0.1 to 2.5% by weight, based on monomers(B1) and (B2).

The polymerization temperature is generally in the range from 30 to 200°C., preferably in the range from 50 to 150° C. and more preferably inthe range from 75 to 110° C.

The polymerization is customarily carried out under atmosphericpressure, but can also take place under reduced or elevated pressure,for example at 1 and 5 bar.

The graft polymers according to the invention are very useful as dyetransfer inhibitors in the washing of colored textiles. They are notonly effective in inhibiting dye transfer, but are also universallyusable and incorporable in a wide range of laundry detergents andcompatible with the customary laundry detergent components.

The graft polymers according to the invention are generally used inamounts from 0.05 to 5% by weight and preferably from 0.1 to 2% byweight in laundry detergent formulations. They are suitable not only forheavy duty detergents but also for specialty detergents, such as colordetergents. In color detergents, which are benign to colors, they arecustomarily used in amounts from 0.1 to 1.5% by weight and preferablyfrom 0.2 to 1% by weight.

The laundry detergents can be pulverulent or be present as a liquidbrand. They contain the customarily used anionic and/or nonionicsurfactants in amounts of from 2 to 50% by weight and preferably from 8to 30% by weight. Particular preference is given to producingphosphate-free or reduced-phosphate laundry detergents, which contain aphosphate content of not more than 25% by weight, reckoned aspentasodium triphosphate. The laundry detergents can also be present ingranular form or as compacts, which have a density in the range from 500to 950 g/l.

Suitable anionic surfactants are for example C₈–C₂₂- and preferablyC₁₀–C₁₈-fatty alcohol sulfates, for example C₉/C₁₁-alcohol sulfates,C₁₂/C₁₃-alcohol sulfates, cetyl sulfate, myristyl sulfate, palmitylsulfate, stearyl sulfate and tallow fatty alcohol sulfate.

Further suitable anionic surfactants are sulfated alkoxylated C₈–C₂₂-and preferably C₁₀–C₁₈-alcohols and soluble salts thereof. Compounds ofthis kind are prepared for example by initially alkoxylating the alcoholand then sulfating the alkoxylation product. The alkoxylation ispreferably carried out using ethylene oxide in an amount from 2 to 50mol and especially from 3 to 20 mol per mole of fatty alcohol. However,the alkoxylation can also be carried out with propylene oxide or withbutylene oxide. It will be appreciated that the alkylene oxides can alsobe used in combination. In that case, the alkoxylated alcohols cancontain the ethylene oxide, propylene oxide and/or butylene oxide unitsin the form of blocks or in random distribution.

Suitable anionic surfactants further include alkylsulfonates, especiallyC₈–C₂₄- and particularly C₁₀–C₁₈-alkylsulfonates, and also soaps, forexample the salts of aliphatic C₈–C₂₄-carboxylic acids.

Further suitable anionic surfactants are linearC₉–C₂₀-alkylbenzenesulfonates (LASs). Their use level can generally beup to 8% by weight.

The anionic surfactants are preferably added to the laundry detergent inthe form of salts. Suitable cations are alkali metal ions, such assodium, potassium and lithium ions, and ammonium ions, for examplehydroxyethylammonium, di(hydroxyethyl)ammonium andtri(hydroxyethyl)ammonium ions.

Examples of suitable nonionic surfactants are alkoxylated C₈–C₂₂- andespecially C₁₀–C₁₈-alcohols. The alkoxylation can be carried out withethylene oxide, propylene oxide and/or butylene oxide. The alkoxylatedalcohols can then contain the alkylene oxide units in the form of blocksor in random distribution. At least one of these alkylene oxides is usedin an amount from 2 to 5 and preferably from 3 to 20 mol per mole ofalcohol. The preferred alkylene oxide is ethylene oxide.

Suitable nonionic surfactants further include C₈–C₂₂- and especiallyC₁₀–C₁₈-alkylpolyglucosides. These compounds contain from 1 to 20 andpreferably from 1.1 to 5 glucoside units.

A further class of suitable nonionic surfactants comprisesN-alkylglucamides of the structures

where D is C₆–C₂₂-alkyl, preferably C₁₀–C₁₈-alkyl, E is hydrogen orC₁–C₄-alkyl, preferably methyl, and G is polyhydroxy-C₅–C₁₂-alkyl havingat least 3 hydroxyl groups, preferably polyhydroxy-C₅–C₆-alkyl.Compounds of this type are obtained, for example, by acylation ofreductively aminated sugars with acyl chlorides of C₁₀–C₁₈-carboxylicacids.

The nonionic surfactants in the laundry detergent formulations arepreferably ethoxylation products of from 3 to 12 mol of ethylene oxidewith C₁₀–C₁₆-alcohols, especially fatty alcohols.

The pulverulent and granular laundry detergents and optionally alsostructured liquid laundry detergents further include one or moreinorganic builders.

Useful inorganic builders include for example all customary compounds,such as aluminosilicates, silicates, carbonates and phosphates.

Examples include specifically aluminosilicates having iron-exchangingproperties, such as zeolites, for example zeolite A, X, B, P, MAP and HSin their sodium form and in forms in which sodium has been partlyexchanged for other cations, such as lithium, potassium, calcium,magnesium or ammonium.

Useful silicates include for example amorphous and crystallinesilicates, such as amorphous disilicates, crystalline disilicates, forexample SKS-6 sheet-silicate from Clariant AG. The silicates can be usedin the form of their alkali metal, alkaline earth metal or ammoniumsalts. Preference is given to using sodium, lithium and magnesiumsilicates.

Carbonates and bicarbonates useful as inorganic builders can likewise beused in the form of their alkali metal, alkaline earth metal andammonium salts. Preference is given to sodium, lithium and magnesiumcarbonates and bicarbonates, and particular preference is given tosodium carbonate and/or sodium bicarbonate. Sodium triphosphate inparticular may be mentioned as a suitable phosphate.

The inorganic builders can be present in the laundry detergents inamounts from 5 to 60% by weight. They can be incorporated into thelaundry detergent, either alone or in any desired combination with eachother. In pulverulent and granular laundry detergents they areincoroporated in amounts from 10 to 60% by weight and preferably from 20to 50% by weight. In structured (multiphase) liquid laundry detergents,inorganic builders are incorporated in amounts of up to 40% by weightand preferably up to 20% by weight. For this purpose, they are suspendedin the liquid formulation ingredients.

The laundry detergents additionally include, as well as the inorganicbuilders, one or more low molecular weight polycarboxylates as organiccobuilders.

Suitable polycarboxylates include for example:

-   -   (1) Polymaleic acids obtainable by polymerization of maleic        anhydride in aromatic hydrocarbons in the presence of        free-radical initiators and subsequent hydrolysis of the        anhydride groups of the polymer. The average molecular weight        M_(w) of these polymaleic acids are preferably in the range from        800 to 5 000.    -   (2) Copolymers of unsaturated C₄–C₈-dicarboxylic acids, such as        maleic acid, fumaric acid, itaconic acid and citraconic acid,        preferably maleic acid, useful comonomers being        -   (i) monoethylenically unsaturated C₃–C₈-monocarboxylic            acids, such as acrylic acid, methacrylic acid, crotonic acid            and vinylacetic acid, preferably acrylic acid and            methacrylic acid,        -   (ii) C₂–C₂₂-monoolefins, vinyl C₁–C₈-alkyl ethers, styrene,            vinyl esters of C₁–C₈-carboxylic acids, (meth)acrylamide and            vinylpyrrolidone, preferably C₂–C₆-α-olefins, vinyl            C₁–C₄-alykl ethers, vinyl acetate and vinyl propionate,            hydroxyalkyl acrylates, such as hydroxyethyl acrylate,            hydroxy-n-propyl acrylate, hydroxy-n-butyl acrylate,            hydroxyisobutyl acrylate, hydroxyethyl methacrylate,            hydroxypropyl methacrylate and hydroxyisopropyl acrylate,        -   (iii) (meth)acrylic esters of monohydric C₁–C₈-alcohols,            (meth)acrylonitrile, (meth)acrylamides of C₁–C₈-alkylamines,            N-vinylformamide and N-vinylimidazole.

The copolymers can contain units derived from the monomers of group

-   -   (i) in amounts up to 95% by weight, derived from monomers    -   (ii) in amounts of up to 60% by weight and derived from monomers    -   (iii) in amounts of up to 20% by weight.

The copolymers can contain units derived from 2, 3, 4 or optionally even5 different monomers.

When the copolymers of group (ii) contain units derived from vinyl esterand vinylformamide monomers, these units may also be partially orcompletely hydrolyzed to form respectively vinyl alcohol and vinylamineunits.

Preferred copolymers of dicarboxylic acids are:

-   -   copolymers of maleic acid and acrylic acid in a weight ratio of        from 10:90 to 95:5, and particularly preferably from 30:70 to        90:10 and having average molecular weights M_(w) especially up        to 10 000, in particular from 1 000 to 6 000,    -   terpolymers of maleic acid, acrylic acid and a vinyl ester of a        C₁–C₃-carboxylic acid in a weight ratio of from 10 (maleic        acid): 90 (acrylic acid+vinyl ester) to 95:10, the weight ratio        of acrylic acid to vinyl ester being in the range from 20:80 to        80:20,    -   especially terpolymers of maleic acid, acrylic acid and vinyl        formate, vinyl acetate or vinyl propionate in a weight ratio of        from 20 (maleic acid): 80 (acrylic acid+vinyl ester) to 90:10,        the weight ratio of acrylic acid to vinyl ester being in the        range from 30:70 to 70:30, having average molecular weights        M_(w) especially up to 10 000, in particular from 1 000 to 7        000,    -   copolymers of maleic acid with C₂–C₈-α-olefins, preferably        ethylene, propylene, isobutene and diisobutene, in a molar ratio        of from 40:60 to 80:20, preferably 50:50, having average        molecular weights M_(w) especially of from 1 000 to 7 000.

-   (3) Graft polymers of unsaturated carboxylic acids on low molecular    weight carbohydrates or hydrogenated carbohydrates.

Suitable unsaturated carboxylic acids are for example maleic acid,fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylicacid, crotonic acid and vinylacetic acid and also mixtures of acrylicand maleic acid, which are grafted onto the grafting base in amountsfrom 40 to 95% by weight for example. For modification, it isadditionally possible for up to 30% by weight, based on the component tobe grafted, of further monoethylenically unsaturated monomers to bepresent in copolymerized form. Suitable modifying monomers are theabovementioned monomers of groups (ii) and (iii) and alsoacrylamido-2-methylpropanesulfonic acid and sodium vinylsulfonate.

Suitable grafting bases include degraded polysaccharides, for exampleacidic or enzymatically degraded starches, inulins or cellulose, reduced(hydrogenated or reductively aminated) degraded polysaccharides, forexample mannitol, sorbitol, aminosorbitol and glucamine, sugars, forexample glucose, and also polyalkylene glycols having average molecularweights M_(w) of up to 5 000, for example polyethylene, glycols,ethylene oxide-propylene oxide block copolymers, ethylene oxide-butyleneoxide block copolymers, random ethylene oxide-propylene oxide copolymersand random ethylene oxide-butylene oxide copolymers, and alkoxylatedmono- and polyhydric C₁–C₂₂-alcohols.

Preference among this group is given to grafted degraded or reducedstarches and grafted polyethylene oxides, the amount of monomer used inthe graft polymerization being in the range from 20 to 80% by weight,based on the graft component. Grafting is preferably performed using amixture of maleic acid and acrylic acid in the ratio of from 90:10 to10:90. The average molecular weights M_(w) of these graft polymers arepreferably up to 10 000 and especially in the range from 1 000 to 7 000.

-   (4) Polyglyoxylic acids having differently structured end groups and    average molecular weights M_(w) of up 10 000, especially from 1 000    to 7 000.-   (5) Polyamidocarboxylic acids and modified polyamidocarboxylic    acids.

Preference is given to using polyaspartic acids and cocondensates ofaspartic acid with further amino acids, C₄–C₂₅-monocarboxylic and-dicarboxylic acids or C₄–C₂₅-monoamines and -diamines. Particularpreference is given to using polyaspartic acids prepared inphosphorus-containing acids and modified with C₆–C₂₂-mono- or-dicarboxylic acids or with C₆–C₂₂-mono- or -diamines. Very particularpreference is given to those modified polyaspartic acids which areobtainable by condensation of aspartic acid with from 5 to 25 mol %,based on aspartic acid, of tridecylamine or oleylamine and at least 5%by weight, based on aspartic acid, of phosphoric acid or phosphorousacid at from 150 to 230° C. and hydrolysis and neutralization of thecocondensates. The average molecular weights M_(w) of thesepolycondensates are preferably up to 10 000 and especially in the rangefrom 1 000 to 7 000.

-   (6) Condensation products of citric acid with hydroxycarboxylic    acids or polyhydroxy compounds having average molecular weights    M_(w) of up to 10 000 and preferably up to 5 000.

The organic cobuilders are present in the pulverulent and granular andalso in the structured liquid laundry detergent formulations in amountsfrom 0.5 to 15% by weight and preferably from 1 to 8% by weight. Theyare present in liquid laundry detergent formulations in amounts from 0.5to 20% by weight, preferably from 1 to 10% by weight and particularlypreferably from 1.5 to 7.5% by weight.

The pulverulent and granular heavy duty laundry detergents additionallyinclude a bleaching system comprising at least one bleaching agent withor without a bleach activator and/or a bleach catalyst. Suitablebleaching agents are perborates and percarbonates in the form of theiralkali metal salts, especially their sodium salts. They are present inthe formulations in amounts from 5 to 30% by weight and preferably from10 to 25% by weight.

Further suitable bleaching agents are inorganic and organic peracids inthe form of their alkali metal or magnesium salts or partly also in theform of the free acids. Examples of suitable organic percarboxylic acidsand salts thereof are magnesium monoperphthalate, phthalimidopercaproicacid and dodecane-1,10-diperacid. An example of an inorganic peracidsalt is potassium peroxomonosulfate (Oxone).

Suitable bleach activators are for example:

-   -   acylamines, such as tetraacetylethylenediamine,        tetraacetylglycoluril, N,N′-diacetyl-N,N′-dimethylurea and        1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine,    -   acylated lactams, such as acetylcaprolactam, octanoylcaprolactam        and benzoylcaprolactam,    -   substituted phenol esters of carboxylic acids, such as sodium        acetoxybenzenesulfonate, sodium octanoyloxybenzenesulfonate and        sodium nonanoyloxybenzenesulfonate,    -   acylated sugars, such as pentaacetylglucose,    -   anthranil derivatives, such as 2-methylanthranil and        2-phenylanthranil,    -   enol esters, such as isopropenyl acetate,    -   oxime esters, such as O-acetylacetone oxime,    -   carboxylic anhydrides, such as phthalic anhydride and acetic        anhydride.

Preference is given to using tetraacetylethylenediamine and sodiumnonanoyloxybenzenesulfonates as bleach activators.

Bleach activators are included in heavy duty laundry detergents inamounts from 0.1 to 15% by weight, preferably in amounts from 1 to 8% byweight and more preferably in amounts from 1.5 to 6% by weight.

Suitable bleach catalysts are quaternized imines and sulfonimines andmanganese complexes. When bleach catalysts are used in the laundrydetergent formulations, they are included in amounts of up to 1.5% byweight and preferably up to 0.5% by weight and in the case of the veryactive manganese complexes in amounts of up to 0.1% by weight.

The laundry detergents preferably include an enzyme system. Customaryenzymes are proteases, lipases, amylases or cellulases. Enzyme systemcan be limited to a single enzyme or comprise a combination of differentenzymes. Laundry detergents include commercially available enzymesgenerally in amounts from 0.1 to 1.5% by weight and preferably from 0.2to 1% by weight of the commercial form. Suitable proteases are forexample Savinase and Esperase (from Novo Nordisk), a suitable lipase isfor example Lipolase (from Novo Nordisk) and a suitable cellulase is forexample Celluzym (again from Novo Nordisk).

The laundry detergents preferably include soil release polymers and/orsoil antiredeposition agents. These are for example polyesters of analcohol component comprising polyethylene oxides singly tipped withdihydric and/or higher alcohols, especially ethylene glycol and/orpropylene glycol, and an acid component comprising aromatic dicarboxylicacids or aromatic and aliphatic dicarboxylic acids.

Useful soil release polymers further include amphiphilic graft andcopolymers of vinyl and/or acrylic esters on or with polyalkylene oxidesand modified celluloses, for example methylcellulose,hydroxypropylcellulose and carboxymethylcellulose.

Soil release polymers which are preferably used are graft polymers ofvinyl acetate on polyethylene oxide of average molecular weight M_(w) 2500–8 000 in a weight ratio from 1.2:1 to 3:1 and also commerciallyavailable polyethylene terephthalate-polyoxyethylene terephthalates ofan average molecular weight M_(w) of from 3 000 to 25 000 formed frompolyethylene oxides having an average molecular weight M_(w) of from 750to 5 000 with terephthalic acid and ethylene oxide and a molar ratio ofpolyethylene terephthalate to polyoxyethylene terephthalate of from 8:1to 1:1 and block polycondensates containing blocks of (a) ester units ofpolyalkylene glycols having an average molecular weight M_(w) of from500 to 7 500 and aliphatic dicarboxylic acids and/ormonohydroxymonocarboxylic acids and (b) ester units of aromaticdicarboxylic acids and polyhydric alcohols. These amphiphilic blockpolymers have average molecular weights M_(w) of from 1 500 to 25 000.

Soil antideposition agents and soil release polymers are included in thelaundry detergent formulations in amounts from 0 to 2.5% by weight,preferably from 0.2 to 1.5% by weight and more preferably from 0.3 to1.2% by weight.

EXAMPLES I) Preparation of Graft Polymers According to Invention

The K values reported in the examples were determined by the method ofH. Fikentscher, Cellulose-Chemie, Volume 13, 58–64, 71–74 (1932), at 25°C. in 1% by weight aqueous solution, unless otherwise stated.

Example 1

In a reactor equipped with nitrogen supply, reflux condenser, stirrerand metering means, 80 g of polyethylene glycol having an averagemolecular weight M_(n) of 1 500 and 80 g of water were heated to aninternal temperature of about 85° C. under nitrogen. The additions werethen commenced of a mixture of 192 g of vinylpyrrolidone, 128 g ofvinylimidazole and 2.4 g of mercaptoethanol, added continuously over 4h, and concurrently 2 g of 2,2′-azobis(2-methylpropionamidine)dihydrochloride (V-50, Wako Chemicals) in 50 g of water, addedcontinuously over 5 h. Afterwards, the mixture was stirred at 85° C. for1 hour. Following addition of 100 g of water and cooling to 60° C., 2.86g of tert-butyl hydroperoxide were added. A start was also made on the30 minute continuous addition of 2 g of sodium disulfite in 50 g ofwater. Afterwards, the mixture was stirred at 60° C. for 1 hour. It wasthen heated to 100° C. before a steam distillation was carried out (1h). A solution was obtained which had a K value (in 3% by weight NaClsolution) of 21.9 and a solids content of 40% by weight.

Example 2

In a reactor equipped with nitrogen supply, reflux condenser, stirrerand metering means, 120 g of polyethylene glycol having an averagemolecular weight M, of 9 000 and 120 g of water were heated to aninternal temperature of about 80° C. under nitrogen. The addition wasthen commenced of a mixture of 257.6 g of vinylpyrrolidone, 22.4 g ofvinylimidazole and 2.8 g of mercaptoethanol. This was done by initiallyadding 5% by weight of this mixture all at once and the rest after 15min continuously over 7 h. Concurrently with the first addition of thismixture, the continuous 7 hour addition of 3.5 g oftert-butylperpivalate in 60 g of isopropanol was commenced. Oncompletion of this addition the mixture was stirred at 80° C. for afurther 2 h. Subsequently, a further 1.4 g of tert-butyl perpivalate in8 g of isopropanol were added before further mixing at 80° C. for 2 h.This last step was repeated 2 more times. The mixture was then heated to100° C. before a steam distillation was carried out for 1 h. 410 g ofwater were added to obtain a solution having a K value of 28.2 and asolids content of 31.9% by weight.

Example 3

Example 2 was repeated, except that 80 g of the polyethylene glycol and80 g of water, a mixture of 224 g of vinylpyrrolidone, 96 g ofvinylimidazole and 3.2 g of mercaptoethanol and also 4 g of tert-butylperpivalate in 60 g of isopropanol and a further 1.6 g of tert-butylperpivalate in 8 g of isopropanol (repeated twice) were used. 100 g ofwater were added to obtain a solution having a K value of 31.4 and asolids content of 43.5% by weight.

Example 4

Example 2 was repeated, except that 80 g of a propylene oxide-ethyleneoxide-propylene oxide triblock copolymer having an ethylene oxidecontent of 40 mol% and an average molecular weight M_(n) of 2 800 and 80g of water, a mixture of 224 g of vinylpyrrolidone, 96 g ofvinylimidazole and 3.2 g of mercaptoethanol and also 4 g of tert-butylperpivalate in 60 g of isopropanol and a further 1.6 g of tert-butylperpivalate in 8 g of isopropanol (repeated twice) were used. Inaddition, 50 g of water were added following the first addition oftert-butyl perpivalate. This afforded a solution having a K value of20.6 and a solids content of 50.2% by weight.

Example 5

Example 2 was repeated, except that 120 g of a polyethylene glycolhaving an average molecular weight M_(n) of 1 500 and 120 g of water, amixture of 140 g of vinylpyrrolidone, 140 g of vinylimidazole and 2.8 gof mercaptoethanol and also 3.5 g of tert-butyl perpivalate in 60 g ofisopropanol and a further 1.4 g of tert-butyl perpivalate in 8 g ofisopropanol (repeated twice) were used. This afforded a solution havinga K value of 23.1 and a solids content of 41.9% by weight.

Example 6

Example 2 was repeated, except that 80 g of a polyethylene glycol havingan average molecular weight M, of 600 and 80 g of water, a mixture of160 g of vinylpyrrolidone, 160 g of vinylimidazole and 3.2 g ofmercaptoethanol and also 4 g of tert-butyl perpivalate in 60 g ofisopropanol and a further 1.6 g of tert-butyl perpivalate in 8 g ofisopropanol (repeated twice) were used. In addition, 100 g of water wereadded following the first addition of tert-butyl perpivalate. 200 g ofwater were added to obtain a solution having a solids content of 32.3%by weight.

Example 7

Example 6 was repeated, except that 80 g of an ethylenediamine-ethyleneoxide-propylene oxide block copolymer having an ethylene oxide contentof 60 mol % and an average molecular weight M_(n) of 6 000 were used.This afforded a solution having a K value of 24.3 and a solids contentsof 41.5% by weight.

Example 8

Example 2 was repeated, except that 40 g of a polypropylene glycolhaving an average molecular weight M_(n) of about 2 000 and 40 g ofwater, a mixture of 180 g of vinylpyrrolidone, 180 g of vinylimidazoleand 3.6 g of mercaptoethanol and also 4.5 g of tert-butyl perpivalate in60 g of isopropanol and a further 1.8 g of tert-butyl perpivalate in 8 gof isopropanol (repeated twice) were used. This afforded a solutionhaving a K value of 23.5 and a solids content of 40.9% by weight.

Example 9

In a reactor equipped with nitrogen supply, reflux condenser, stirrerand metering means, 100 g of polyethylene glycol having an averagemolecular weight M_(n) of 6 000 and 200 g of water were heated to anexternal temperature of about 100° C. (oil bath) under nitrogen.Thereafter, 95 g of N-vinylimidazole and 5 g of N-vinylpyrrolidone wereadded continuously over 4 h while concurrently 5 g of2,2′-azobis(2-methylpropionamidine) dihydrochloride (V-50, WakoChemicals) in 100 g of water were added continuously over 5 h. This wasfollowed by slow cooling to 60° C. On attainment of this temperature (inthe reactor) 0.7 g of tert-butyl hydroperoxide and 0.5 g of sodiumdisulfite in 20 g of water were added over 30 min. After cooling to roomtemperature, 134 g of dimethyl sulfate were added over 2 h while coolingwith ice. After renewed heating to 70° C. for 2 h, the polymerizationended. A further 53 g of water were added to obtain a clear solutionhaving a K value (in 0.5 molar NaCl solution) of 47.9 and a solidscontent of 50.0% by weight.

Example 10

Example 9 was repeated, except that 5 g of tert-butyl perpivalate in 100g of isopropanol were used as free-radical initiator. Finally, 77 g ofwater were added to obtain a clear solution having a K value (in 0.5molar NaCl solution) of 79.2 and a solids content of 45.7% by weight.

Example 11

In a reactor equipped with nitrogen supply, reflux condenser, stirrerand metering means, 100 g of polyethylene glycol having an averagemolecular weight M_(n) of 1 500 and 200 g of water were heated to anexternal temperature of about 100° C. (oil bath) under nitrogen.Thereafter, 97 g of N-vinylimidazole and 3 g of N-vinylpyrrolidone werecontinuously added over 4 h, while concurrently 5 g of tert-butylperpivalate in 100 g of isopropanol were added continuously over 5 h.After further stirring at that temperature for one hour, the mixture wascooled down to 75° C. On attainment of this temperature (in the reactor)0.7 g of tert-butyl hydroperxide and 0.5 g of sodium disulfite in 20 gof water were added over 30 min. Following a steam distillation (500 gof distillate) the reaction mixture was maintained at 85° C.(externally) for a further 2 h. A further 20 g of water were added toobtain a clear solution having a K value (in 0.5 molar NaCl solution) of22.4 and a solids content of 52.4% by weight.

Example 12

In a reactor equipped with nitrogen supply, reflux condenser, stirrerand metering means, 100 g of polyethylene glycol having an averagemolecular weight M_(n) of 1 500 and 100 g of water were heated to anexternal temperature of about 100° C. (oil bath) under nitrogen.Thereafter, 90 g of N-vinylimidazole and 10 g of N-vinylpyrrolidone wereadded continuously over 4 h, while concurrently 5 g of2,2′-azobis(2-methylbutyronitrile) (V-59, Wako Chemicals) in 100 g ofisopropanol were added continuously over 5 h. Following addition of afurther 0.5 g of 2,2′-azobis(2-methylbutyronitrile) the reaction mixturewas stirred for a further 1 h. A steam distillation yielded 700 ml ofdistillate. Water was added to obtain a solution having a K value (in0.5 molar NaCl solution) of 19.1 and a solids content of 29.6% byweight.

Example 13

In a reactor equipped with nitrogen supply, reflux condenser, stirrerand metering means, 130 g of diethyl sulfate were added over 2 h to340.7 g of the product of example 11 under nitrogen. The mixture wasthen heated to 70° C. and stirred at that temperature for a further 2 h.This afforded a solution having a K value (in 0.5 molar NaCl solution)of 18.5 and a solids content of 43.6% by weight.

Example 14

In a reactor equipped with nitrogen supply, reflux condenser, stirrerand metering means, 124.6 g of benzyl chloride were added over 1.5 h to340.7 g of the product of example 12 under nitrogen. The mixture wasthen heated to 70° C. and stirred at that temperature for a further 2 h.This afforded a solution having a K value (in 0.5 molar NaCl solution)of 21.5.

Example 15

In a reactor equipped with nitrogen supply, reflux condenser, stirrerand metering means, 80 g of a random 2-(2-butoxyethoxy)ethanol-ethyleneoxide-propylene oxide copolymer (molar ratio 1:13:22) having an averagemolecular weight M_(n) of 2 000 and 450 g of water were heated to aninternal temperature of about 85° C. under nitrogen. Thereafter, amixture of 192 g of vinylpyrrolidone and 128 g of vinylimidazole and,commencing 5 minutes later, a mixture of 6.4 g of2,2′-azobis(2-methylpropionamidine) dihydrochloride (V-50, WakoChemicals) and 50 g of water were each added continuously over 2 h. Thiswas followed by stirring at 85° C. for a further 1 h. After cooling toan internal temperature of 60° C. initially 2.29 g of tert-butylhydroperoxide were added all at once, followed by 1.60 g of sodiumdisulfite in 50 g of water added continuously over 4.5 h. Followingsupplementary stirring at 60° C. for 1 hour, the reaction mixture washeated to 100° C. and subjected to a steam distillation (1h). Thisafforded a solution having a K value of 43.2 and a solids content of31.6% by weight.

II) Testing of Graft Polymers According to the Invention as Dye TransferInhibitors in Laundry Detergents

The graft polymers according to the invention were tested as dyetransfer inhibitors in laundry detergents. To this end, a granularlaundry detergent (LD 1) and two liquid laundry detergents (LD 2, and LD3) were prepared by way of example in the composition recited in table1, and they each contained 0.15% by weight of graft polymer. Whitecotton test cloth was then washed under the conditions mentioned intable 2 in the presence of dye which was added to the wash liquor as a0.03 or 0.06% by weight aqueous solution.

The staining of the test cloth was measured photometrically using anElrepho 2000 photometer from Datacolor. The reflectance (in %) wasmeasured at the wavelength of the absorption peak of each of the variousdyes. The whiteness of the test cloth after washing was used to evaluatethe degree of staining. The measurements reported in tables 3a–crepresent averages of multiple replications.

Tables 3a–c also recite the results of comparative wash trials carriedout without dye transfer inhibitor (V1) or using as dye transferinhibitor (V2) a graft polymer prepared similarly to example 2 ofDE-A-100 36 713 using a polyethylene glycol having an average molecularweight M_(n) of 9 000.

TABLE 1 Composition of laundry detergents (LD) 1 LD 2 LD 3 Amount AmountAmount in % by in % by in % by Ingredients weight weight weightC₁₂/C₁₄-fatty alcohol sulfate 27 C₁₂/C₁₄-fatty alcohol 7 ethoxylateCitric acid 2 C₁₂/C₁₄-alkylbenzenesulfonate 9 10 C₁₃/C₁₅-tallow fattyalcohol 6.6 6 12 converted with 7 EO coconut fatty acid 5 11.4 KOH 1.7Borax 2.2 2.3 Propylene glycol monomethyl 10 ether Ethanol 2.0 Soap 1.81.4 3.4 Zeolite A 45 Polycarboxylate (acrylic 5 acid-maleic acidcopolymer (w/w 70:30, M_(w) 70 000) Magnesium silicate 0.8 Sodiumcarbonate 7.0 2.3 Trisodium citrate × 2 H₂O 12 0.6Carboxymethylcellulose, 0.8 sodium salt Graft polymer (calc. 100%) 0.150.15 0.15 Water ad 100 ad 100 ad 100

TABLE 2 Wash conditions LD 1 LDs 2 and 3 Apparatus Launder-O-meterLaunder-O-meter Cycles 1 1 Duration 30 min 30 min Water hardness 3.0mmol of 3.0 mmol of Ca²⁺/l, molar Ca²⁺/l, molar ratio ratio Ca:Mg:HCO₃:Ca:Mg:HCO₃: 4:1:8 4:1:8 Temperature 60° C. 60° C. Dye input Dye solutionDye solution Test cloth Cotton swatch Cotton swatch Liquid quantity 250ml 250 ml Liquor ratio 12.5:1 12.5:1 Detergent concentration 4.5 g/l 6g/l

TABLE 3A LD 1 wash results % % % Graft reflectance reflectancereflectance polymer of Direct Blue Direct Red Direct Black Ex. 71 212 221 76.9 65.4 71.0 2 63.4 57.1 64.8 3 69.4 62.2 69.3 4 68.8 61.7 68.0 572.9 61.3 70.6 6 74.9 64.7 71.6 7 75.5 65.1 71.8 8 77.2 65.9 71.7 V1 (no56.1 53.6 60.7 addition) V2 58.5 54.8 57.1 Whiteness 79.8 78.8 80.0before wash

TABLE 3B LD2 wash results % % % Graft reflectance reflectancereflectance polymer of Direct Blue Direct Red Direct Black Ex. 71 212 221 69.4 57.9 74.8 2 67.4 57.8 69.3 3 68.3 58.2 71.4 4 68.0 57.8 71.5 V1(no 57.0 54.2 68.0 addition) V2 58.4 54.2 67.1 Whiteness 79.8 78.8 80.0before wash

TABLE 3C LD3 wash results 3 % % % Graft reflectance reflectancereflectance polymer of Direct Blue Direct Red Direct Black Ex. 71 212 225 78.8 71.0 77.9 6 76.5 68.6 76.8 7 77.0 69.4 76.1 8 77.9 71.2 76.4 V1(no 65.4 52.3 69.5 addition) V2 68.9 52.8 69.1 Whiteness 79.8 78.8 80.0before wash

The wash results obtained document the excellent effectiveness of thegraft polymers according to the invention as dye transfer inhibitors,and this effectiveness is independent of the type of dye.

1. Graft polymers comprising: (A) a polymeric polyether grafting basedevoid of monoethylenically unsaturated units, and (B) polymeric sidechains formed from copolymers of two different monoethylenicallyunsaturated monomers (B1) and (B2) which each comprises at least onenitrogeneous heterocycle, wherein said side chains (B) account for 60 to95% by weight of the total polymer; wherein (B1) is a cyclicN-vinylamide of the formula I

where R is C₁–C₅-alkyl, and R¹ is hydrogen or C₁–C₄-alkyl; and whereinsaid monomer (B2) contains a nitrogenous heterocycle selected from thegroup consisting of the pyrroles, pyrrolidines, pyridines, quinolines,isoquinolines, purines, pyrazoles, imidazoles, triazoles, tetrazoles,indolizines, pyridazines, pyrimidines, pyrazines, indoles, isoindoles,oxazoles, oxazolidones, oxazolidines, morpholines, piperazines,piperidines, isoxazoles, thiazoles, isothiazoles, indoxyls, isatins,dioxindoles and hydantoins and derivatives thereof, and barbituric acidand uracil and derivatives thereof.
 2. Graft polymers as claimed inclaim 1, wherein said monomer (B1) is N-vinylpyrrolidone.
 3. Graftpolymers as claimed in claim 1, wherein said monomer (B2) is selectedfrom the group consisting of the N-vinylimidazoles,alkylvinylimidazoles, 3-vinylimidazole N-oxides, 2- and4-vinylpyridines, 2- and 4-vinylpyridine N-oxides, N-vinylcaprolactamsand N-vinyloxazolidones, and the betainic derivatives and quaternizationproducts thereof.
 4. Graft polymers as claimed in claim 1, wherein saidmonomer (B2) is a vinylimidazole of the formula IIa or IIb or avinylpyridine of the formula IIc, IId, IIe or IIf

where R², R³, R⁴ and R⁶ are each independently hydrogen, C₁–C₄-alkyl orphenyl, R⁵ is C₁–C₂₀-alkylene, X⁻ is —SO₃ ⁻, —OSO₃ ⁻, —COO⁻, —OPO(OH)O⁻,—OPO(OR′)O⁻ or —PO(OH)O⁻ and R′ is C₁–C₆-alkyl.
 5. Graft polymers asclaimed in claim 1, wherein the weight ratio of said monomers (B1) and(B2) is in the range from 99:1 to 1:99.
 6. Graft polymers as claimed inclaim 1, wherein said grafting base (A) is a polyether having an averagemolecular weight M_(n) of at least 300 and the formula IIIa or IIIb

where independently R⁷ is hydroxyl, amino, C₁–C₂₄-alkoxy, R¹³—COO—,R¹³—NH—COO— or a polyalcohol radical, R⁸, R⁹ and R¹⁰, which may be thesame or different, are each —(CH₂)₂—, —(CH₂)₃—, —(CH₂)₄—, —CH₂—CH(CH₃)—,—CH₂—CH(CH₂—CH₃)— or —CH₂—CHOR¹⁴—CH₂—, R¹¹ is hydrogen,amino-C₁–C₆-alkyl, C₁–C₂₄-alkyl, R¹³—CO— or R¹³—NH—CO—, R¹² isC₁–C₂₀-alkylene whose carbon chain may be interrupted by from 1 to 10oxygen atoms in ether function, R¹³ is C₁–C₂₄-alkyl, R¹⁴ is hydrogen,C₁–C₂₄-alkyl or R¹³—CO—, A is —CO—O—, —CO—B—CO—O— or —CO—NH—B—NH—CO—O—,B is —(CH₂)_(t)— or substituted or unsubstituted arylene, n is 1 or,when R⁷ is a polyalcohol radical, is from 1 to 8, s is from 0 to 500, tis from 1 to 12, each u, which may be the same or different, is from 1to 5,000, each v, which may be the same or different, is from 0 to5,000, and each w, which may be the same or different, is from 0 to5,000.
 7. Graft polymers as claimed in claim 1, wherein said graftingbase (A) is selected from the group consisting of polyalkylene oxides,singly capped polyalkylene oxides, afie doubly capped polyalkyleneoxides, and mixtures thereof.
 8. A process for preparing graft polymersas claimed in claim 1, which comprises: free-radically polymerizing saidmonomers (B1) and (B2) in the presence of said grafting base (A).
 9. Alaundry detergent, comprising: at least one graft copolymer as claimedin claim
 1. 10. A method, which comprises: mixing the laundry detergentof claim 9 with water and soaking fabric in the laundry detergent andwater mixture.
 11. The method as claimed in claim 10, wherein said sidechains (B) account for 70 to 95% by weight of the total polymer.
 12. Themethod as claimed in claim 10, wherein said side chains (B) account for70 to 90% by weight of the total polymer.
 13. The laundry detergent asclaimed in claim 9, wherein said side chains (B) account for 70 to 95%by weight of the total polymer.
 14. The laundry detergent as claimed inclaim 9, wherein said side chains (B) account for 70 to 90% by weight ofthe total polymer.
 15. A method, which comprises: contacting at leastone graft copolymer as claimed in claim 1 with fabric.
 16. The method asclaimed in claim 15, wherein said side chains (B) account for 70 to 95%by weight of the total polymer.
 17. The method as claimed in claim 15,wherein said side chains (B) account for 70 to 90% by weight of thetotal polymer.
 18. Graft polymers as claimed in claim 1, wherein saidside chains (B) account for 70 to 95% by weight of the total polymer.19. Graft polymers as claimed in claim 1, wherein said side chains (B)account for 70 to 90% by weight of the total polymer.